Diepoxide polymers



United States Patent 2,932,626 DIEPOXIDE POLYMERS Benjamin Phillips andPaul S. Starcher, Charleston, and Charles W. McGary, Jr., and Charles T.Patrick, In, South Charleston, W. Va., assignors to Union CarbideCorporation, a corporation of New York No Drawing. Application March 7,1957 Serial No. 644,461

32 Claims. (c1. 260--78.4)

This invention relates to curable compositions and resinous compositionsmade therefrom. More particularly, this invention is directed to novelamine-epoxide compositionswhich are useful in the synthetic resins artas adhesives, protective coatings, castings, laminates, films and thelike, and to methods for their preparation. This application is acontinuation-in-part of application, Serial No. 588,601, filed June 1,1956, now US. Patent No. 2,917,491, issued December 15, 1959.

Epoxide resins have been made heretofore from mixtures of amines andpolyglycidyl ethers of polyhydric phenols. These resins have achieved adegree of usefulness in the synthetic resins art but are limited bycertain inherent characteristics to a restricted field of application.The viscosities of these mixtures are so high (of the order of 9,000centipoises and higher at 25 C. without solvents or diluents) as topreclude easy handling and application. For example, in making castingsfrom these mixtures extreme care and, many times, special equipment arerequired in order to obtain bubble-free castings. Although reactivediluents can be used, there are the disadvantages of higher cost andprobable lower strength properties of resins made from these mixtures.The use of solvents is undesirable because of the likelihood of bubbleformation in the resin when the solvent is driven oif during curing andthe dangers brought about by solvent fumes. It is also difficult tosuccessfully incorporate fillers and pigments in these mixtures.Mixtures of amines and polyglycidyl ethers of polyhydric phenols havebeen found heretofore to have extremely short potlives. In some casescuring at room temperature takes place before a homogeneous mixture ofamine and polyglycidyl ether can be obtained. This is particularlydisadvantageous in that the period of time permissable for working andapplying the mixture is very short and in some cases negligible.Non-uniform resins are obtained in such cases because of the inabilityto form homogeneous amine-epoxide mixtures prior to curing. Suchmixtures are additionally disadvantageous in that, even when theirpot-lives are sufficiently long to permit the attainment of homogenity,they can not be maintained in workable form for long periods. Thisentails the necessity of maintaining quantities of unmixed amine on handwhich is accompanied by the dangers of the well-known toxicity andnoxiousness associated with amines. The inconvenience of periodicallypreparing such amine-epoxide mixtures can be costly, time-consuming anddangerous.

Our curable compositions comprise mixtures of polyfunctional amines andbis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylates hereinafter tobe referred to also as the diepoxide. By the term polyfunctional amine,as used herein, is meant an amine having at least two active aminohydrogen atoms which can be on the same nitrogen or on differentnitrogen atoms. Certain of our compositions are mobile liquids havinglow viscosities (from 300 to 1,000 centipoises at 26 C.) and areparticularly capable of being easily prepared and conveniently appliedto form bubble-free resins. Various "ice fillers and pigments can bereadily incorporated into our compositions to provide variegatedphysical effects. Certain other curable compositions of this inventionare solids which can be reduced to liquid form by heating withoutincurring substantial curing as long as heating is not prolonged forlonger than about 1 to 2 hours. All of our compositions are storable forlong periods of time, of more than one week, without hardening orappreciable increases in viscosity. They can be rapidly cured by addingsmall amounts of acidic catalysts or by the application of heat withoutcatalysts or by both measures. These curable compositions can bepartially cured to form solid, partially polymerized resins which can bepulverized or ground to make molding and casting compounds. Such castingand molding compounds can be stored without refrigeration for longperiods of up to a year and longer after which time they can be moldedor otherwise shaped and fully cured by the application of heat. Thepartially cured resin may also be dissolved in a suitable solvent, suchas xylene or methyl-isobutyl ketone and used as surface coating whichcan be subsequently heat cured.

The resins of this invention are solvent-resistant, tough products. Theycan be made as transparent products or can be'colored with suitablepigments and as uniform, infusible products free of bubbles or otherdiscontinuities. These resins can be also made with a wide range offlexibilities and rigidities. Products having properties which aretailor-made for specific requirements of flexibility and rigidity canthus be produced. Our resins adhere tenaciously to many materials andexhibit only negligible shrinkage during their formation by curing. Suchresins are useful in many applications including the manufacture ofvarious articles, such as door knobs, brush handies, small structuralparts for instrument cabinets and electronic components for use inguided missles and high speed aircraft, and as protective coatings formany materials, such as wood, glass and metal.

Our curable compositions can be readily prepared by mixing apolyfunctional amine with a bis(3,4-epoxycyclohexylmethyl) hydrocarbondicarboxylate and treating, as by stirring to obtain a homogeneousmixture or solution. When a solid or highly viscous amine is employedheating is advantageous in facilitating the formation of a solution. Inany event the application of heat may be used to aid in bringing aboutsolution although it should not be prolonged to the extent thatsubstantial curing takes place. Acid catalysts can be added at thispoint or at any point prior to curing or not at all, as desired.Catalyst concentrations can be varied over a wide range depending uponthe rate of cure desired. Concentrations of up to 10 Weight percentbased on the weight of diepoxide have been found to be advantageousCatalyst concentrations as low as 0.05 weight percent based on theweight of diepoxide have been found to provide appreciable catalyticeffects.

Our resins can be prepared from these curable compositions by theapplication of heat. The curing can be carried out by maintaining thecurable compositions at temperatures in the range from 30 C. to 250 C.Tent;- peratures higher than 250 C. can be used although somediscoloration which may not be desired may be brought about in theresins thus formed. The time for effecting the complete cure can be madeto vary from several minutes to several hours depending upon theselection of curing temperatures. A higher curing temperature willprovide a resin in less time than a low curing temperature. It ispreferred, however, to heat the curable compositions at a temperaturewithin the range from 50 C. to 150 C. to first partially cure thecomposition. A temperature from C. to 200 C. then can be used tocomplete the cure. However, any one or combination of two or moretemperatures'within the above-specified range of 30 C. to 250 C. can beemployed, if desired, to effect the full cure.

While not wishing to be held to any particular theory or mechanics ofreaction, it is believed that in curing, one epoxy group of thediepoxide molecule reacts with a maximum of one amino hydrogen of thepolyfunctional amine molecule with the formation of a hydroxyl groupattached to the diepoxide molecule and a carbon to nitrogen to carbonlinkage interconnecting the amine and 'diepoxide molecules. Thus,according to this belief, a polyfunctional amine having more than 2amino hydrogens to the molecule would cross-link through carbon tonitrogen to carbon linkages. Also according to our observations a degreeof etherification occurs from intermolecular reactions of two or moreepoxy groups with each other and from intermolecular reactions of anepoxy group with a hydroxyl group formed in the abovenoted manner by aprevious reaction of an epoxy group with an amino hydrogen. Thus,additional cross-linking through carbon to oxygen to carbon linkages isthought to be effected by these intermolecular reactions between epoxygroups or epoxy groups and hydroxyl groups. Tough, solid resins havebeen obtained by curing our curable compositions which contain suchrelative proportions of polyfunctional amine andbis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylates as providefrom 0.4 to 4.0 amino hydrogens of the amine for each epoxy group fromthe diepoxide. Hard, tough, infusible resins have been obtained from ourcurable compositions containing such relative amounts of polyfunctionalamine and bis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylate asprovide from 0.7 to 2.0 amino hydrogens of the amine for each epoxygroup of the diepoxide. Resins "produced from our curable compositionscontaining 1 to 3 amino hydrogens per epoxy group have been found to beuseful as anion exchange resins. Hardenable epoxide resins can beobtained from our curable compositions, for example, those containingless than 0.4 amino hydrogen per epoxy group. Such hardenable resins canbe polymerized with active hydrogen compounds, e.g., polyamines,polyhydric alcohols or phenols, polycarbox- 'ylic acids and the like orpolycarboxylic anhydrides to form useful products or they can be used asplasticizers and/ or stabilizers for chlorine containing resins. Epoxideresinous hardeners can also be made from our curable compositions,particularly those containing more than 4.0 amino hydrogens per epoxygroup. These resinous hardeners can be used to harden the manypolyepoxides 'to produce useful products. Resins having difi'erentphysical properties can be produced by curing our compositions whichcontain amounts of amine'and diepoxide providing difierent ratios ofamino hydrogens to epoxy groups.

Bis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylates arehydrocarbon dicarboxylic acid diesters of 3,4-epoxycyclohexylmethanol orlower alkyl substituted 3,4-epoxycyclohexylmethanols wherein thecarboxyl groups of the dicarboxylic acid are esterified by the alcohols.By the term lower alkyl, as used herein, is meant an alkyl group havingfrom one to 6 carbon atoms. They include such diesters asbis(3,4-epoxycyclohexylmethyl) oxalate, succinate, adipate,terephthalate, maleate, sebacate, pimelate, as well as the lower alkylring substituted diesters, e.g., his(3,4-epoxy-6-methylhexylmethyl),bis(3,4-epoxy-l-methylcyclohexylmethyl), bis-(3,4-epoxy-2-methylcyclohexylmethyl), bis(3,4-epoxy-3-methylcyclohexylmethyl) hydrocarbon dicarboxylates and the like; Theseand other bis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylates aredescribed in US. Patent No. 2,750,395. Preferredbis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylates are thosewhich can be made from hydrocarbon dicarboxylic acids having from 2 to12 carbon atoms to the molecule and 3,4-epoxycyclohexylmethanols whichhave no ring subs stituents or not more than 5 lower alkyl ringsubstituents on any one cyclohexane ring.

Bis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylates can beprepared by the epoxidation of bis(3- cyclohexenylmethyl) hydrocarbondicarboxylates with a suitable epoxidizing agent using methods known inthe art. Advantageous methods for making these diepoxides are describedin US. Patent No. 2,750,395. However, other suitable methods may beused, if desired.

Polyfunctional amines are typified by the aliphatic primary amines, suchas, ethylamine, isopropylamine, nbutylarnine, isobutylamine,Z-ethylhexylamine, monoethanolamine, monoisopropanolamine, beta alanine,amides, e.g., formamide, acetamide, propionamide, nbutyramide,stearamides, hexahydrobenzamide, and the like; aromatic primary amines,such as, aniline, paramethylbenzylamine, and the like; heterocyclicprimary amines, such as, N-(aminoethyl) morpholine, N-(aminopropyl)morpholine, and the like, the aliphatic polyamines, such as,ethylenediamine, propylenediamines, butylenediamines, pentylenediamines,hexylenediarnines, octylenediamines, nonylenediamines,decylenediarnines, dimethylurea, 1,3-diamino-2-propano1,3,3-irninobispropylamine, guanidine and the like; aromatic polyamines,such as meta-, ortho-, and para-phenylenediamines, 1,4-naphthalenediamine, 1,4-anthradiamine, 3,3-biphenyldiamine,3,4-biphenyldiamine, 3,4-toluenediamine, metaxy-lylenediamine, alpha,alpha'-bi-para-toluidine, para, para-methylenedianiline,1-methoxy-6-methyl-meta-phenylenediamine, para, para'-sul fonyldianilineand the like; and heterocyclic polyamines, such as piperazine,2,5-dimethylpiperazine, melamine, 2,4-diamine-5-(aminomethyl)pyrimidine, 2,4,6-triaminopyrimidine, 3,9-bis'(amino ethyl)spirobi-metadioxane, the polyalkylene polyamines, in particular, thepolyethylene polyamines and polypro- 'pylene polyamines, such asdiethylenetriamine, triethylenetetramine, tetraethylenepentarnine,dipropylenetriamine and the like.

Other polyfunctional amines include the low molecular weight polyamideswhich are condensation products of polycarboxylic acids, in particular,hydrocarbon dicarboxylic acids, with polyamines, particularly, diamines,

such as those monomeric diamines previously listed. Typical polyamidescan be prepared in accordance with known'condensation procedures fromadipic, acid and hexamethylenediamine, dilinoleic acid andethylenediamine, terephthalic acid and diethylenetriamine and the like.

Still other illustrations of polyfunctional amines are the additionproducts ofpolyamines, in particular diamines, and triamines, and lowmolecular weight epoxides containing oxirane oxygen linked to vicinalcarbon atoms, such as, ethylene-oxide, propylene oxide, butadienedioxide, diglycidyl ether, epoxidized soybean oil, epoxidized saffloweroil, and the like, and polyglycidyl polyethers, such as those preparedfrom polyhydric phenols and .epichlorhydrin. Particularly usefulpolyfunctional amines are the mono-hydroxyalkyl polyalkylene polyamineswhich can be prepared by the addition reaction of polyalkylenepolyamines, preferably, ethylenediamine, propylenediamine,diethylenetriamine, dipropylenetriamine @or triethylenetetramine and thelike, with ethylene oxide or propylene oxide. This reaction can beconducted under pressure at temperatures of 50 C. or 55 C. to boilinginthe absence of solvents or in the presence ofjwater or an alcohol.However, the reaction is more advantageously carried out at temperaturesbelow 40 C. and preferably below 35 C. without pressure. The amines soproduced include N-hydroxyethylethylenediamine,N-hydroxypropyldiethylenetriamine, N-hydroxyethylpropylenediamine, Nhydroxypropylpropylenediamine, N-hydroxyethyldipropylenetriamine, andthe like. Other polyfunctional amines can be prepared with knownprocedures by the addition reaction of polyglycidyl poly- ,ethers ofdihydric phenols and polyamines, in particular,

fiolyalkylene polyamines. .Of particular importance in forming theseepoxide polyamine adductsare the di glycidyl diethers of dihydr'icphenols, such as for example, the homologues ofdihydroxydiphenylmethanes singularly or mixed and thedihydroxydiphenyldimethylmethanes singularly or mixed. Mixtures ofdiglycidyl diethers of dihydric phenols can be prepared by reactingepichlorhydrin with a dihydric phenol using a molar excess ofepichlorhydrin over the theoretical molar requirement. Substantiallypure cuts of the diglycidyl diethers then can be obtained by fractionaldistillation under reduced pressure, for example. Illustratively, thepolyfunctional amine, i.e., the epoxide polyamine adduct, itself can beprepared by mixing the diglycidyl polyether of a dihydric phenol with apolyalkylene diamine such as diethylenetriamine, dipropylenetriamine,and the like, bringing to an elevated. temperature, for example, up toabout 200 C. and maintaining at such an elevated temperature for aperiod of from 4 to 5 hours. Alternatively, as an illustration,polyfiunctional aminescan be prepared by adding a diglycidyl diether ofa dihydric phenol to a polyalkylene polyamine over a period of time,around three to four hours, while maintaining the reaction mixture at anelevated temperature, for example, up to about 200 C. and subsequentlyadding a dihydric phenol.

Additional polyfunctional amines include the low molecular weightaddition products of a polyamine, preferably a polyalkylene polyaminesuch as those listed above, and a vinyl group-containing compound;Typical vinyl group-containing compounds are ethylene, propylene, 1-butene, isobutene, acrolein, vinyl chloride, vinyl acetate,acrylonitrile, styrene and the like. These polyfunctional amines can beprepared in accordance with known procedures by reacting a polyamine anda vinyl group- -containing compound in various proportions at atemperature in the range from 20 C. to 100 C. and removing unreactedmaterials and. low boiling materials by vacuum distillation.

Other polyfunctional amines having a total of at least two active aminohydrogen atoms to the molecule can be advantageously employed in theepoxide compositions of this invention. For example, such polyfunctionalamines as mixtures of para,para'-methylenedianiline andmeta-phenylenediamine, or other mixtures of two or more polyfunctionalamines, can be used. Particularly valuable compositions made inaccordance with this invention are obtainable from such polyfunctionalamines as described above which have melting points or melting pointranges below about 150 C. and contain at least two amino nitrogens toeach of which at least one amino hydrogen is attached. I

Acid catalysts which can be employed in our curabl compositions toincrease the curing rate are the metal halide Lewis acids, e.g., borontrifluoride, stannic chloride, ferric chloride, or metal halide Lewisacid-amine complexes, as, for example, piperidine-boron trifiuoridecomplex and monoethylamineboron trifluoride complex. Uniform dispersionsof catalyst in our curable compositions prior to curing have been foundto be desirable in order tominirnize local curing around catalystparticles. Agitation of the curable composition as the catalystis addedis sutlicient when the catalyst is miscible with the composition. Whenthe two are immiscible, the catalyst can be added in a solvent. Typicalsolvents for the acid catalysts include organic ethers, e.g., diethylether, dipropyl ether, organic esters, e.g., methyl acetate, ethylpropionate, organic ketones, e.g., acetone, cyclohexanone, organicalcohols, e.g., methanol, propylene glycol, and the like.

Our curable compositions may contain small amounts of epoxides anddiepoxides other than bis(3,4-epoxycyclohexylmethyl) hydrocarbondicarboxylates for developing special properties in our resins. Inaddition, other active hydrogen containing compounds, such as phenolsand alcohols, or polycarboxylic anhydrides, can be incorporated into ourcurable compositions to provide special elfects.

The following illustrative examples are presented. Wherever appearing inthese examples, heat distortion values were obtained at 264 pounds persquare inch of stress in accordance with ASTM test method D-648-45T.Barcol hardness values presented in the examples were determined throughthe use of a Barcol Impressor GYZI 934-4 at a temperature of 25 C.unless otherwise indicated. Izod impact values as presented in theexamples were obtained in accordance with ASTM test method, D-256-47T ata temperature of 25 C. unless otherwise indicated.

EXAMPLE 1 Two hundred and forty pounds of epichlorhydrin, 64 pounds ofethyl alcohol and pounds of 4,4-dihydroxydiphenyldimethylmethane,hereinafter referred to as bisphenol A, were charged to a stainlesssteel still equipped with a high speed agitator and reflux condenser andthe mixture was heated to 60 C. at 325 to 350 millimeters of mercury,absolute pressure. Eighty-two pounds of 50 weight percent aqueous NaOHwas then gradually added, with vigorous agitation, over a 3.5 hourperiod at such a rate that the reaction mass temperature remained belowabout 65 C. The reaction mass was stirred an additional 0.5 hour. Thenthe alcohol and unreacted epichlorhydrin were removed by vacuumdistillation at 50 millimeters pressure to a pot temperature of 70 C.followed by a vacuum steam distillation for 15 minutes at 70 C. to 80 C.at 50 millimeters pressure leaving a viscous residue. The residue wasthen dissolved in toluene and the toluene solution washed withsuccessive portions of water at 45 C. to 55 C. until the wash water wassubstantially neutral. The washed residue then was heated at an absolutepressure of 75 millimeters of mercury to a temperature of C. to removeany residual toluene and vacuum steam distilled for 15 minutes at anabsolute pressure of 50 millimeters of mercury and a temperature of C.It was then vacuum dehydrated at an absolute pressure of 50 millimetersof mercury and a temperature of 140 C., cooled and discharged. Thepolyglycidyl polyether of bisphenol A prepared in this manner had aspecific gravity of 1.16 grams per cubic centimeter at 25 C., aviscosity as determined in a Brookfield viscosimeter of 15,000centipoises at 25 C. and an epoxy equivalent of grams of polyglycidylpolyether per mole of epoxy group.

EXAMPLE 2 Four hundred and seventy-five grams (1.25 moles) of apolyglycidyl polyester of bisphenol A, such as that produced in Example1 were added slowly and with vigorous agitation to 515 grams (5 moles)of diethylenetriamine. The addition rate was adjusted and coolingapplied as needed to keep the reaction mass below a temperature of about75 C. The product produced in this manner had a viscosity of 9,000centipoises at 25 C., a specific gravity of 1.07 at 25 C. and an amineequivalent of about 50 grams of product for each amino hydrogen atomcontained by the product.

EMMPLES 3 THROUGH 8 of polyamine and diepoxide employed in each of thesemixtures were such as to provide the amino hydrogen to epoxy groupratios correspondingly listed in Table I. The mixtures of Examples 3through 5 were heated at 130 C. for 13 hours. The mixtures of Examples 6through 8 were heated at 120 Cftor 11.5 hours and then at160 C; for anaddrtlonal 6 hours. lnfuslble resms were obtained from all mixtures, theproperties of sard resins beingllsted 1n the table below. Table 1 AminoWeight Weight Hy- Example of Die- Polya-mine of Polydrogen Resm Numberpoxide amine Per Properties (Grams) (Grams) Epoxy Group 3 3. 42Dlethylene- 0. 60 1. 5 Hard.

triarnine. 4 3. 42 m-Phenyl- 0. 81 1. 5 Barcol enedihardness amine. of39. 6 4. 00 Polyamlne 1. 00 0. 9 Barcol prepared hardness V in Ex- 0f38. ample 1. 6 1. 92 1,6-Hexane- 0. 68 2. 0 Hard.

diamine. 7 1. 92 Ethylene- 0. 2. 0 Do.

diamine. 8 1. 92 m-Xylene- 0. 73 2. 0 Do.

diamine.

EXAMPLE 9 A mixture was prepared from 4.18 grams of bis(3,4-epoxy-6-methylcyclohexylmethyl) sebacate and 0.6 gram ofdiethylenetriamine. The mixture contained such proportions of polyamineand diepoxide as provided 1.5 amino hydrogens for each epoxy group. Themixture was then heated at 160 C. for about 6 hours. A soft, flexible,amber-colored resin was obtained.

EXAMPLES 10 THROUGH 16 Seven mixtures, each containing 1.22 grams ofbis(3,4- epoxy-6-methylcyclohexylmethyl) succinate and variousproportions of diethylenetriamine as listed in Table 11 below, wereprepared. The relative amounts of polyamine and diepoxide contained byeach of these mixtures were such as to provide the amino hydrogen toepoxy amounts of diethylenetn'amine as correspondingly listed in TableIII, were prepared, These mixtures each contained" such relativeamountsof polyamine and .diepoxide as provided the amino hydrogen toepoxy group ratios as listed in Table III. Each mixture was thenmaintained at 120 C. for the periods of time listed in Table III. Gelswere formed from the mixtures of Examples 17 through 19 in 6 hoursheating at 120 C. All mixtures were then subjected to an additional cureat 160 C. for an additional 6 hours. Resins having the propertiescorrespondingly listed in Table III were ob tained.

Table 111 Weight of Amino Oure at Example Polyamine Hydrogen 120 0.Resin Properties Number (Grams) Per Epoxy (Hours) Group 0.210 1.50 7Hard, lnfusible.

0. 420 3.00 48. 5 Hard.

EXAMPLES 23 THROUGH 27 120 C. until gels were formed, the respectivegels form-- ing in the times listed in Table IV. Each gel was heated at160 C. for an additional 2 hours. Infusible resins 0 having theproperties listed in the table below were obgroup ratios as listed inTable 11. Each mixture was then tained.

Table IV Example Weight of Weight of Gel Number Diepoinde DrepoxldePolyamine Polyarnine Time Resin Properties (Grams) (Grams) (Hours) 2 3.Bis (3,4-epoxy-6-methylcyclo- 4. 0 Polyamiue pre- 1.0 2. 67 amber,opaque, Barcol hexylmethyl) succmate. parerli in Exhardness of 18. amp e2 24 BIS (3,4-epoxycyclohexylmethy1) 4. 0 .do 1. 5 2.28 amber, opaque,Barcol terephthalate. hardness of 33. 25 Bis(3,4-ep0xy-6-methy1cycl0-4.0 do 1.5 2. 47 yellow, opaque, tough,

hexylmethyl) adlpate. Bfaeol hardness o 0. 2eBis(3,4-epoxy-6-methy1cyclo- 4.5 do 1. 5' 3.50 yellow, opaque tough,hexylmethyl) sebacate. Barcol ahrdness of 0. 27Bis(2%,?-ep0xycyclohexy1methyl) 4.0 m-Xylenediamine... 1. 5 0.08 amber,hard.

are a e.

heated at 120 C. for 23.5 hours. The temperature was then raised to 160C. and maintained thereat for an additional 4 hours. Resins having theproperties listed in TableII were obtained.

' EXAMPLES 17 THROUGH 22 Six mixtures, each containing 1.22 grams ofbis(3,4-

epoxy--methylcyclohexylmethyl) succinate and various What is claimed is:

1. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)hydrocarbon dicarboxylate having at least one lower, alkyl substituenton each cyclohexane ring thereof and a polyfunctional amine in suchrelative proportions as provide from 0.4 to 4.0 amino hydrogens of thepolyamine for each epoxy group of the bis(3,4epoxycyclohexylmethyl)hydrocarbon dicarboxylate.

21A curable composition comprising bis(3,4-epoxycyclohexylmethyl)hydrocarbon dicarboxylate having at least one lower alkyl substituent oneach cyclohexane ring thereof and a polyfunctional amine in such,relative proportions as provide from 0.7 to 2.0 amino hydrogens of thepolyamine for each epoxy group of the bis(3,4- epoxycyclohexylmethyl)hydrocarbon dicarboxylate.

3. A curable composition comprising bis(3,4-epoxycyelohexylmethyl)hydrocarbon dicarboxylate and apolyfunctional amine in such relativeproportions as provide from 0.4 to 4.0 amino hydrogens of the polyaminefor 9 each epoxy group of the bis(3,4-epoxycyclohexylmethyl) hydrocarbondicarboxylate.

4. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)hydrocarbon dicarboxylate and a polyfunctional amine in such relativeproportions as provide from 0.7 to 2.0 amino hydrogens of the polyaminefor each epoxy group of the bis(3,4-epoxycyclohexylmethyl) hydrocarbondicarboxylate.

5. A curable composition comprising bis(3,4-epoxy-6-methylcyclohexylmethyl) hydrocarbon dicarboxylate and a polyfunctionalamine in such relative proportions as provide from 0.4 to 4.0 aminohydrogens of the polyamine for each epoxy group of thebis(3,4-epoXy-6-methylcyclohexylmethyl) hydrocarbon dicarboxylate.

6. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)oxalate and a polyfunctional amine in such relative proportions asprovide from 0.4 to 4.0 amino hydrogens of the polyamine for each epoxygroup of the bis(3,4-epoxycyclohexylmethyl) oxalate.

7. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)terephthalate and a polyfunctional amine in such relative proportions asprovide from 0.4 to 4.0 amino hydrogens of the polyamine for each epoxygroup of the bis(3,4-epoxycyclohexylmethyl) terephthtalate.

8. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)adipate and a polyfunctional amine in such relative proportions asprovide from 0.4 to 4.0 amino hydrogens of the polyamine for each epoxygroup of the bis(3,4-epoxycyclohexylmcthyl) adipate.

9. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)sebacate and a polyfunctional amine in such relative proportions asprovide from 0.4 to 4.0 amino hydrogens of the polyamine for each epoxygroup of the bis(3,4-epoxycyclohexylmethyl) sebacate.

10. A curable composition comprising bis(3, 4-epoxycyclohexylmethyl)succinate and a polyfunctional amine in such relative proportions asprovide from 0.4 to 4.0 amino hydrogens of the polyamine for each epoxygroup of the bis(3,4-epoxycyclohexylmethyl) succinate.

11. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)hydrocarbon dicarboxylates and a polyfunctional amine from the class ofdiethylenetriamine, m-phenylenediamine, 1,6-hexanediamine,ethylenediamine, and m-xylenediamine, in such relative proportions asprovide 0.4 to 4.0 amino hydrogens of the amine for each epoxy group ofbis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxylate.

12. A curable composition comprising bis(3,4-epoxy-6-methylcyclohexylmethyl) succinate and a polyfunctionalamine from theclass of diethylenetriamine, m-phenylenediamine, 1,6-hexanediamine,ethylenediamine and mxylenediamine, in such relative proportions asprovide 0.4

to 4.0 amino hydrogens of the amine for each epoxy group ofbis(3,4-epoxy-6-methylcyclohexyhnethyl) succinate.

13. A curable composition comprising bis(3,4-epoxy-6-methylcyclohexylmethyl) sebacate and diethylenetriamine in suchrelative proportions as provide from 0.4 to 4.0 amino hydrogens of thepolyamine for each epoxy .10 group of thebis(3,4-epoxy-6-methylcyclohexylmethyl sebacate.

14. A curable composition comprising bis(3,4-epoxy-6-methylcyclohexylmethyl) succinate and diethylenetriamine in suchrelative proportions as provide from 0.4 to 4.0 amino hydrogens of thepolyamine for each epoxy group of thebis(3,4-epoxy-6-methylcyclohexylmethyl) succinate.

15. A curable composition comprising bis(3,4-epoxycyclohexylmethyl)oxalate and m-xylenediamine in such relative proportions as provide from0.4 to 4.0 amino hydrogens of the polyamine for each epoxy group of thebis(3,4-epoxycyclohexylmethyl) oxalate.

16. A curable composition comprising bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate and diethylenetriamine in suchrelative proportions as provide from 0.4 to 4.0 amino hydrogens of thepolyamine for each epoxy group of thebis(3,4-epoxy-6-methylcyclohexylmethyl) adipate.

17. The resin obtained by heating the curable composition of claim 1.

18. The resin obtained by heating the curable composition of claim 2.

19. The resin obtained by heating the curable composition of claim 3.

20. The resin obtained by heating the curable composition of claim 4.

21. The resin obtained by heating the curable composition of claim 5.

22. The resin obtained by heating the curable composition of claim 6.

23. The resin obtained by heating the curable composition of claim 7.

24. The resin obtained by heating the curable compo sition of claim 8.

25. The resin obtained by heating the curable composition of claim 9.

26. The resin obtained by heating the curable composition of claim 10.

27. The resin obtained by heating the curable composition of claim 11.

28. The resin obtained by sition of claim 12.

29. The resin obetained by heating the curable composition of claim 13.

30. The resin obtained by heating the curable composition of claim 14.

31. The resin obtained by heating the curable composition of claim 15.

32. The resin obtained by heating the curable composition of claim 16.

heating the curable compo- References Cited in the file of this patentUNITED STATES PATENTS 2,136,928 Schlack Nov. 15, 1938 2,444,333 CastanJune 29, 1948 2,585,115 Greenlee Feb. 12, 1952 2,750,395 Phillips et a1.June 12, 1956

1. A CURABLE COMPOSITION COMPRISING BIS(3,4-EPOXYCYCLOHEXYLMETHYL)HYDROCARBON DICARBOXYLATE HAVING AT LEAST ONE LOWER ALKYL SUBSTITUENT ONEACH CYCLOHEXANE RING THEREOF AND A POLYFUNCTIONAL AMINE IN SUCHRELATIVE PROPORTIONS AS PROVIDE FROM 0.4 TO 4.0 AMINO HYDROGENS OF THEPOLYAMINE FOR EACH EPOXY GROUP OF THE BIS(3,4EPOXYCYCLOHEXYLMETHYL)HYDROCARBON DICARBOXYLATE.